KR101566768B1 - Resin composition for printed wiring board - Google Patents

Abstract

(A) a polyimide resin having a hexafluoroisopropanol group and a siloxane structure, and (B) a thermosetting resin, wherein the resin composition is excellent in solvent resistance, exhibits a small temperature change in modulus of elasticity, .

Description

[0001] Resin composition for printed wiring board [0002]

The present invention relates to a resin composition for a printed wiring board containing (A) a polyimide resin having a hexafluoroisopropanol group and a siloxane structure, and (B) a thermosetting resin.

Polyimide resins having excellent heat resistance are widely used in the fields of electronics and aerospace.

Heretofore, a material having both heat resistance and low elasticity has been developed by introducing a siloxane structure into the polyimide resin (Patent Document 1). However, the solvent resistance was not necessarily satisfactory.

In order to solve this problem, it has been reported that a composition containing a polyimide resin having a siloxane structure and a phenolic hydroxyl group and an epoxy resin is useful as an adhesive for printed wiring boards and the like (Patent Document 2). However, the change in modulus of elasticity with temperature change was not necessarily satisfactory. Also, in combination with the thermosetting resin, the warpage and cracks of the printed wiring board were worried, which was not satisfactory.

Japanese Patent Application Laid-Open No. 2002-12666 Japanese Laid-Open Patent Publication No. 2004-51794

The object of the present invention is to provide a resin composition containing a polyimide resin having a siloxane structure and a thermosetting resin, wherein the resin composition for a printed wiring board has both excellent heat resistance and solvent resistance and is more reliable.

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the present inventors have found that a resin composition containing a siloxane structure-containing polyimide resin having a hexafluoroisopropanol group introduced therein and a thermosetting resin exhibits a small change in modulus of elasticity with temperature change, Excellent properties, and excellent as an insulating material for printed wiring boards, thereby completing the present invention.

That is, the present invention includes the following contents.

(1) A resin composition for a printed wiring board, which contains (A) a polyimide resin having a hexafluoroisopropanol group and a siloxane structure, and (B) a thermosetting resin.

(2) The resin composition for a printed wiring board according to the above item (1), further comprising (C) an inorganic filler.

(3) The resin composition for a printed wiring board according to (1) or (2) above, wherein the thermosetting resin is an epoxy resin.

(4) The resin composition for a printed wiring board according to any one of (1) to (3), wherein the polyimide resin has repeating units represented by the following general formulas (1) and (2).

In the above Formulas 1 and 2,

R1 is a tetravalent organic group,

R2 is a divalent diamine residue having a hexafluoroisopropanol group,

R3 is a divalent siloxane diamine residue,

The repeating number M in one molecule of the repeating unit represented by the formula (1) is an integer of 1 to 100,

The repeating number N in one molecule of the repeating unit represented by the general formula (2) is an integer of 1 or more and 100 or less.

(5) The method according to any one of (1) to (4) above, wherein (A) the functional group equivalent of the hexafluoroisopropanol group of the hexafluoroisopropanol group and the polyimide resin having the siloxane structure ) Is 1000 to 10000 g / mol.

(6) The printed wiring board according to any one of (1) to (5) above, wherein the polyimide resin (A) having a hexafluoroisopropanol group and a siloxane structure has a siloxane content of 50 to 80% / RTI >

(7) A solder resist ink containing the resin composition according to any one of (1) to (6).

(8) An adhesive film comprising the resin composition according to any one of (1) to (6) above formed on a support.

(9) An adhesive film with a metal foil, wherein the resin composition according to any one of (1) to (6) above is formed on a metal foil.

(10) A prepreg obtained by impregnating the sheet-like fiber base material with the resin composition according to any one of (1) to (6) above.

(11) A prepreg with metal foil, wherein a metal foil is laminated on the prepreg according to (10) above.

(12) A coverlay film in which the resin composition according to any one of (1) to (6) above is layered on a heat resistant film.

(13) The printed wiring board, wherein the insulating layer contains the resin composition for a printed wiring board according to any one of (1) to (6).

(14) The printed wiring board according to (13), wherein the insulating layer includes a solder resist layer, an interlayer insulating layer and a coverlay layer.

(15) A printed wiring board in which a solder resist layer is formed by the solder resist ink described in (7) above.

(16) A printed wiring board in which a solder resist layer is formed by the adhesive film according to (8).

(17) A printed wiring board in which an interlayer insulating layer is formed by the adhesive film according to (8).

(18) A printed wiring board in which an interlayer insulating layer and / or a conductor layer is formed by the adhesive film with a metal foil according to (9).

(19) A printed wiring board in which an interlayer insulating layer is formed by the prepreg according to (10).

(20) A printed wiring board in which an interlayer insulating layer and / or a conductor layer is formed by the metal foil-attached prepreg according to (11).

(21) A printed wiring board in which a coverlay layer is formed by the coverlay film according to (12).

INDUSTRIAL APPLICABILITY The resin composition containing the polyimide resin and the thermosetting resin of the present invention has low elasticity and excellent heat resistance and solvent resistance. By using the resin composition, the resin composition is excellent in solvent resistance, It is possible to provide a resin composition for an excellent printed wiring board.

The present invention relates to a resin composition for a printed wiring board containing (A) a polyimide resin having a hexafluoroisopropanol group and a siloxane structure, and (B) a thermosetting resin.

Hereinafter, the present invention will be described on the basis of a preferred embodiment.

The polyimide resin (A) in the present invention has a hexafluoroisopropanol group (hereinafter referred to as HFA group) and a siloxane structure. The polyimide resin preferably has repeating units represented by the following general formulas (1) and (2).

Formula 1

(2)

In the above Formulas 1 and 2,

R1 is a tetravalent organic group,

R2 is a divalent diamine residue having an HFA group,

R3 is a divalent siloxane diamine residue,

The repeating number M in one molecule of the repeating unit represented by the formula (1) is preferably an integer of 1 or more and 100 or less (1? M? 100)

The repeating number N in one molecule of the repeating unit represented by the formula (2) is preferably an integer of 1 or more and 100 or less (1? N? 100).

Examples of the tetravalent organic group represented by R 1 include those having the following structures.

In the above formulas,

A is oxygen, sulfur, CO, SO, SO _2, CH _2, and _{CH (CH 3), C (} CH 3) 2, C (CF 3) 2, or C (CCl _{3) 2,}

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

Examples of the divalent diamine residue having an HFA group represented by R 2 include those having the following structures.

In the above formulas,

A is the same as defined above,

J is an integer of 1 to 4,

K is an integer of 1 to 6,

P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

Examples of the divalent siloxane diamine residue represented by R 3 include those having the following structures.

In the above formulas,

R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,

R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,

a, b and c each independently represents 0 or an integer of 1 or more, and b + c? 1, a + b + c? 60,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

The polyimide resin in the present invention can be produced by reacting the tetrabasic acid dianhydride represented by the general formula (3) with the diamine compound represented by the general formulas (4) and (5).

In the above formulas (3), (4) and (5)

R1, R2 and R3 are the same as defined above.

The tetravalent organic group represented by R 1 in the tetrabasic acid dianhydride represented by the general formula (3) is as described above. Specific examples of the tetravalent organic group represented by R 1 include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 4,4'- (hexafluoroisopropylene) -bis- (phthalic acid dianhydride), 4,4'-oxydiphthalic dianhydride, Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid - ((4,4'-isopropylidene diphenoxy) 1-methylethylidene) -di-4,1-phenylene ester, ethylene glycol bisanhydrotrimellitate, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 9,9- 4-dicarboxyphenyl) fluorene dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- Cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 4- (2 , 5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5- (2,5- Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) 1,2-C] furan-1,3-dione, and the like. These tetrabasic acid dianhydrides can be used in combination of two or more.

Examples of the diamine compound having an HFA group represented by the formula (4) include those represented by the following formulas.

[Chemical Formula 4-a]

[Formula 4-b]

[Chemical formula 4-c]

In the above formulas 4-a, 4-b and 4-c,

A is the same as defined above,

J is an integer of 1 to 4,

K is an integer of 1 to 6,

P and Q are each independently an integer of 0 to 2, 1? (P + Q)? 4,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

In the formula (4-b), the amino group on the naphthalene ring may be bonded to the same benzene ring or may be bonded to different benzene rings. Similarly, when there are plural HFA groups, they may be bonded to the same benzene ring or may be bonded to different benzene rings, respectively.

The diamine compound represented by the formula (4-a) can be produced according to a known method described in WO 2006/043501 pamphlet. The diamine compound represented by the formula (4-c) can be prepared according to a known method described in WO2006 / 041115 pamphlet. The diamine compound represented by the formula (4-b) can be produced by reacting the corresponding naphthalene diamine compound with hexafluoroacetone or hexa-diamine in accordance with a known method described in the pamphlet of International Publication WO 2006/043501 and International Publication WO 2006/041115 pamphlet Fluoroacetone trihydrate to introduce the HFA group onto the naphthalene ring. These diamine compounds having an HFA group can be used in combination of two or more.

The diaminosiloxane represented by the general formula (5) includes those represented by the following formulas.

[Chemical Formula 5a]

In the above formula (5a)

R4 and R5 each independently represent an alkylene group, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms,

R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group,

a, b and c each independently represents 0 or an integer of 1 or more, b + c? 1, a + b + c? 60,

The hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.

The siloxane structure in the present invention is preferably a structure represented by the following formula (5b).

[Chemical Formula 5b]

In the above general formula (5b)

Re and Rf are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, or a phenoxy group,

m is an integer of 60 or more,

Re or Rf may be different for each repeating unit.

Examples of the diaminosiloxane represented by the formula (5a) include 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis , 1,2,2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,1,3,3-tetramethyl Bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetra Phenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis Methyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis Methyl-1,3-bis (4-aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy- , 5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3- ) Trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl- -Dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy- 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy- 1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) , 5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl- And the like. These diaminosiloxanes may be used alone or in combination of two or more.

The diamines other than the diamine compounds represented by the general formulas (4) and (5) may be used alone or in combination of two or more. The diamine compound may be represented by the following formula (6).

In Formula 6,

R11 is a divalent organic group other than a divalent diamine residue having an HFA group and a divalent siloxane diamine residue.

The diamine compound is not particularly limited, and examples thereof include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, Dimino-2,5-dimethylbenzene, and 1,4-diamino-2,5-dihalogenobenzene; diamine compounds containing one benzene ring such as 4,4'-diaminodiphenyl ether, 3,3 Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4'- , 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-amino di Phenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 2,2 Bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'- (4-aminophenyl) cyclohexane, o-dianisidine, o (4-aminophenyl) hexafluoropropane, 2,2'-bis (2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, Aminobenzanilide, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenyl ether , 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminobiphenyl, 3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4 ' -Methylene-bis (2,6-diisopropylaniline), 4,4'-methylene-bis (2-ethyl-6-methylaniline), 3,3'-diethyl-4,4'- Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, - diaminodiphenyl ether, 3,3'- Methoxy-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane , Diamine compounds containing two benzene rings such as 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene and 2,3-diaminonaphthalene, 1,4 Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenyl) benzene, , diamine compounds containing three benzene rings such as α, α'-bis (4-aminophenyl) -1,3-diisopropylbenzene, and diamine compounds containing three benzene rings such as 2,2- ] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- 4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- Aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9- (4-aminophenyl) anthracene, 1,3-diaminopyrene, 1,6-diaminopyrene, etc. A diamine compound having at least four benzene rings, a diamine compound having an alicyclic structure such as 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine) 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- Diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane, diamine compounds having a linear hydrocarbon structure such as baramine 551 (trade name: Cognis D-2000, D-4000, XTJ-500, XTJ-501, XTJ-502 and HK- And diamine compounds having a polyoxyalkylene diamine structure such as XTJ-511, XTJ-504, XTJ-542, XTJ-533 and XTJ-536 (manufactured by Hansen Corporation).

The diaminosiloxane represented by the general formula (5) preferably has an NH ₂ equivalent of 400 to 6000 g / mol, more preferably 400 to 2500 g / mol, further preferably 400 to 1000 g / mol. desirable. When the NH ₂ equivalent is larger than this range, the molecular weight of the siloxane structure is too large to increase the hydrophobicity of the resin, resulting in deterioration of compatibility with the thermosetting resin. In some cases, the resin itself has a difference in polarity between the imide portion and the siloxane portion It becomes excessively large, and it becomes difficult to stably synthesize the resin. On the other hand, when the NH ₂ equivalent is smaller than this range, it is difficult to obtain sufficient flexibility because the molecular weight of the siloxane structure becomes small. Also, it is preferable to contain a phenyl group in view of good compatibility with a thermosetting resin.

The reaction ratio of the quaternary acid dianhydride represented by the general formula (3) to the diamine compound represented by the general formulas (4) and (5) when the diamine compound represented by the general formula (6) is used in combination is the sum of the diamine compounds represented by the general formulas Is not particularly limited and may be any excess, but from the viewpoint of increasing the molecular weight of the obtained resin and improving the mechanical properties, the number of functional groups equivalent to all of the diamine compounds used in the reaction And the number of the functional group equivalents of the tetrabasic acid dianhydride is preferably substantially the same. Specifically, when the number of the functional group equivalent of the acid anhydride group of the quaternary acid dianhydride to be used is represented by X and the number of functional groups equivalent of the amino group of the entire amine compound to be used is represented by Y, 0? | (XY) | / X? The reaction is preferably carried out under the condition of 0 < = (XY) / X < / = 0.1.

The number of functional groups equivalent X (mol) of the acid anhydride group can be obtained from the formula X = B1 / A1, where A1 (g / mol) is the functional group equivalent of the acid anhydride group and B1 (g) That is, the functional group equivalent refers to the molecular weight of the compound per functional group, and the functional group equivalent number refers to the number of functional groups per compound weight (injection amount).

Similarly, the functional group equivalent A2 (g / mol) of the amino group of the HFA group-containing diamine compound represented by the general formula (4), B2 (g) and the functional group equivalent A3 of the amino group of the diaminosiloxane represented by the general formula (B2 / A2) + (B3 / A3) + (B4 / g) where B3 is the injection amount, A4 is the functional group equivalent of the amino group of the diamine compound represented by the formula / A4). ≪ / RTI > The diamine compound represented by the formula (6) is an optional component, and when it is not contained, (B4 / A4) in the above formula is 0.

On the other hand, since the injection ratio of the diamine compounds of the formulas (4) and (5) is reflected in the content of the siloxane structure and the content of the HFA group in the obtained resin, these two values are arbitrarily set, The range of compound injection rates is determined. First, the amount of the siloxane structure contained in the resin to be obtained is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight. When the proportion of the siloxane structure is larger than 90% by weight, the resulting resin becomes more sticky and difficult to handle. Conversely, when it is smaller than 40% by weight, flexibility of the resin becomes insufficient.

(% By weight) = {B3 / (B1 + B2 + B3 + B4-B5)} 100 where the weight of water to be desorbed by imidization is B5, Can be obtained. Here, B5 is obtained by the expression B5 = 18 x W, where W is the smaller of the values of X or Y described above. The diamine compound represented by the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

The upper limit of the content of the siloxane structure is preferably 80% by weight, more preferably 75% by weight, still more preferably 70% by weight, and particularly preferably 65% by weight, from the viewpoint of maintaining heat resistance at a high temperature. On the other hand, the lower limit of the content of the siloxane structure is preferably 50% by weight, more preferably 54% by weight, and even more preferably 58% by weight from the viewpoint of exhibiting flexibility.

The upper limit of the functional group equivalent (hereinafter referred to as HFA group equivalent) of the HFA group of the polyimide resin to be obtained is too small in the amount of the HFA group in the resin, and when the resin composition using the resin is cured, the curing becomes insufficient Mol, more preferably 5,000 g / mol, still more preferably 5,000 g / mol, still more preferably 4,000 g / mol, from the viewpoint of preventing the above-mentioned problems. On the other hand, the lower limit of the HFA group equivalent of the obtained polyimide resin is such that the crosslinking density when the resin composition is cured due to the inclusion of a large amount of the HFA group is increased and the content of the siloxane structure is inevitably decreased, It is more preferably 1000 g / mol, more preferably 2000 g / mol, and still more preferably 2500 g / mol, from the viewpoint of preventing the occurrence of the above-mentioned problems. (G / mol) of the HFA group equivalent of the polyimide resin is represented by V (g / mol) = (B1 + B2 + B3 + B4-B5) H). ≪ / RTI > The diamine compound represented by the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

The terminal of the polyimide resin is considered to be a dicarboxylic group in which an amino group, an acid anhydride group or an acid anhydride group is ring-opened, depending on the reaction ratio of the tetrabasic acid dianhydride and the diamine compound.

The reaction operation is not particularly limited. For example, it is more preferable to carry out the heat dehydration imidization in the polymerization solution in terms of simplicity of operation. Specifically, first, in a solvent in which an HFA group-containing diamine compound and a siloxane diamine are dissolved, an azeotropic solvent such as toluene, xylene or the like is added in an inert gas atmosphere. Then, a tetrabasic acid dianhydride is added and reacted at 80 DEG C or less, preferably 0 to 50 DEG C for 1 to 24 hours to obtain a polyamic acid solution. The obtained polyamic acid solution is heated to 100 to 200 ° C, preferably 150 to 200 ° C, and at this time, the polyimide solution can be obtained by ring-closing the water to be desorbed while azeotropically removing it with toluene. At this time, it was confirmed that almost the theoretical amount of water was distilled off, and that the outflow of water could not be seen. On the other hand, unlike this method, dehydration ring closure reaction of polyamic acid can also be carried out at a low temperature using a mixed acetic anhydride / pyridine solution.

The reaction solvent used in the reaction is not particularly limited as long as it can react with the raw material and the obtained resin, and examples thereof include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, Butyrolactone,? -Valerolactone,? -Caprolactone,? -Caprolactone, ethylene carbonate, propylene carbonate, ethyl cellosolve acetate, butyl cell N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and the like can be used in combination with other solvents such as benzene, toluene, xylene, , And preferably cyclohexanone, gamma -butyrolactone. These solvents may be used alone or in combination of two or more. Particularly, it is more preferable to use an aromatic hydrocarbon solvent such as petroleum naphtha in combination with a solvent such as cyclohexanone or? -Butyrolactone.

Further, the obtained polyimide resin solution may be put into a poor solvent such as water or methanol (poor solvent) to precipitate and precipitate the polymer, and after drying again, the polymer may be redissolved in a solvent according to the application.

The upper limit of the number average molecular weight (Mn) of the polyimide resin in the present invention is preferably 50000, more preferably 40,000 or more, more preferably 30000 or more, in view of preventing the viscosity of the resin composition from increasing and handling property from being lowered. More preferably 25000, still more preferably 20,000, and still more preferably 20,000. On the other hand, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10000, and even more preferably 15000 from the viewpoint of exhibiting the flexibility of the resin composition. The upper limit of the weight average molecular weight (Mw) of the polyimide resin in the present invention is preferably 50000, more preferably 40,000 or more, more preferably 30000 or more, in view of preventing the viscosity of the resin composition from rising and handling property from being lowered. Is more preferable. On the other hand, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10,000, further preferably 15,000, and particularly preferably 20,000 from the viewpoint of exhibiting the flexibility of the resin composition. The number average molecular weight and the weight average molecular weight are values measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the number average molecular weight and the weight average molecular weight by the GPC method were measured by using LC-9A / RID-6A manufactured by Shimadzu Seisakusho Co., Ltd. as a measuring device, Shodex K manufactured by Showa Denko K.K. -800P / K-804L / K-804L as a mobile phase and 0.4% by weight of lithium bromide in N-methylpyrrolidone dissolved therein was measured at a column temperature of 40 ° C and calculated using a calibration curve of standard polystyrene can do.

The resin composition of the present invention contains (B) a thermosetting resin. By mixing the thermosetting resin with the imide resin having the siloxane structure (A) obtained above, it is possible to obtain a thermosetting resin composition exhibiting small curing shrinkage, high flexibility, high heat resistance and adhesiveness. Examples of the thermosetting resin include an epoxy resin, a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, a benzoxazine compound, an amine imide compound, and a cyanate ester compound. At this time, it is preferable to select a thermosetting resin having a functional group capable of reacting with the HFA group contained in the resin (A) skeleton. Among them, an epoxy resin having two or more glycidyl groups is more preferable. Further, a curing agent for epoxy resin, a curing accelerator and the like may be added.

The epoxy resin used in the embodiment of the present invention is not particularly limited as long as it contains two or more glycidyl groups. Examples thereof include glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolak, cresol novolak, etc., glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol, Glycidyl ethers such as glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, glycidyl ethers such as those obtained by substituting glycidyl groups for active hydrogen bonded to nitrogen atoms such as aniline and isocyanuric acid Epoxycyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) Alicyclic epoxy resins such as cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, glycidyl ethers of paraxylylene-modified phenol resins, Len A glycidyl ether of a modified phenolic resin, a glycidyl ether of a terpene-modified phenol resin, a glycidyl ether of a dicyclopentadiene-modified phenol resin, a glycidyl ether of a cyclopentadiene-modified phenolic resin, a polycyclic aromatic ring- Glycidyl ether of a naphthalene ring-containing phenol resin, and biphenyl-type epoxy resin. These may be used singly or in combination of two or more.

The monoepoxy compound may be suitably used in combination with an epoxy compound having at least two epoxy groups in one molecule. Examples of such monoepoxy compounds include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether , Ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, and the like. The epoxy resin to be used is not limited to one type alone, and two or more kinds of epoxy resins may be used in combination.

The epoxy resin curing agent used in the embodiment of the present invention is not particularly limited as long as it hardens the epoxy resin, and examples thereof include a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, a benzoxazine Resins, amine imide resins, cyanate ester compounds, and the like. Of these curing agents, phenolic compounds are particularly preferred.

As the phenolic compound, those having two or more phenolic groups are preferable. Examples of the resin include bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolak resin, cresol novolak resin, paraxylylene denatured phenol resin, meta-xylylene paraxylylene denatured phenol resin, Phenolic resin, dicyclopentadiene-modified phenol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, naphthalene ring-containing phenol resin, biphenyl-type phenol resin and phenazine novolac resin containing triazine structure , Alone or in combination of two or more.

As the carboxylic acid-based compound, those having two or more carboxyl groups are preferable. Examples thereof include organic acids such as terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methylnadic acid, dodecylsuccinic acid, chloridic acid, maleic acid and adipic acid They may be used singly or in combination of two or more.

The acid anhydride-based compound preferably has at least one acid anhydride group. For example, there may be mentioned phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, anhydrous chloridic acid and maleic anhydride. They may be used singly or in combination of two or more.

The amine compound is used as a curing agent for causing addition reaction with an epoxy resin or anionic polymerization of the epoxy resin itself. For example, tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl- Imidazoles such as imidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl- IM-1000 (manufactured by Nikko Kinshoku Kabushiki Kaisha) or IS-1000 (manufactured by Nikko Kinko Kabushiki Kaisha), which is an imidazole silane compound having an imidazole moiety and a silanol moiety together, and 4,4 ' - diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodi Aromatic amine-based compounds such as phenylmethane, 3,3'-aminodiphenylmethane and 3,4'-diaminodiphenylmethane; Aliphatic amine compounds such as m-xylylenediamine, diethylenetriamine and tetraethylenepentamine, and alicyclic amine compounds such as melamine resin and 2-vinyl-4,6-diamino-s- Compounds, dicyandiamide, and the like.

As the benzooxane-based compound, it is preferable to have two or more benzoxadine moieties, and for example, a benzooxazine such as Ba type benzooxadine or Bb type benzoxazine (manufactured by Shikoku Chemical Industry Co., Ltd.) .

The amine imide compound is obtained by reacting a maleimide compound with an amine compound, and particularly preferably has two or more secondary amino groups. For example, it is possible to use a copolymer of a methacrylic acid and a methacrylic acid, such as Technomite E2020 And the like.

As the cyanate ester compound, those having two or more cyanate groups are preferable, and examples thereof include Primaset BADCY, Primaset BA230S and Primaset LECY manufactured by RONDER Japan K.K.

The epoxy resin curing accelerator used in the embodiment of the present invention is not particularly limited. For example, phosphorus compounds such as triphenylphosphine, triphenylphosphonium triphenylborate, and tetraphenylphosphonium tetraphenylborate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6- Dimethylaminomethyl) phenol, and other tertiary amines such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, Imidazoles such as methylimidazole and 1-cyanoethyl-2-methylimidazole, and dicyandiamide.

The blending amount of the thermosetting resin in the resin composition varies depending on the specific type thereof, but is generally from 1 to 200 parts by mass, (B) the thermosetting resin relative to 100 parts by mass of (A) the polyimide resin, And preferably 5 to 100 parts by mass. If the blending amount of the thermosetting resin is too small, the curing will be insufficient and the chemical resistance and heat resistance may be deteriorated. If too large, the flexibility may be insufficient. The chemical equivalent ratio of the sum of the epoxy resin curing agent and the siloxane-containing polyimide resin having a HFA group in the skeleton to the epoxy resin is not particularly limited, but is preferably set in the range of 0.7 to 1.3, more preferably 0.8 to 1.2 More preferable. By controlling the content in this range, it is possible to control the unreacted contents of each of the functional groups to a smaller extent and to make the chemical resistance, electric characteristics and the like better. Further, even when a siloxane resin is separately blended with a polyimide resin containing no HFA group and siloxane and a thermosetting resin, the compatibility tends to be poor. By using a polyimide resin containing an HFA group and a siloxane structure, The compatibility tends to be improved.

In the resin composition of the present invention, (C) an inorganic filler is preferably blended. The combination of the inorganic filler exhibits effects such as preparation of viscosity characteristics before curing, preparation of the modulus of elasticity after curing, improvement of strength, and reduction of thermal expansion rate. Examples of the inorganic filler include silica, alumina, mica, kaolin, silicate, barium sulfate, magnesium hydroxide and titanium oxide. Silica and alumina are preferable, and silica is particularly preferable. From the viewpoint of insulation reliability, the inorganic filler preferably has an average particle diameter of 3 mu m or less, more preferably 1.5 mu m or less, and more preferably 1 mu m or less. The average particle diameter can be measured by a laser diffraction / scattering type particle size distribution analyzer LA-500 (trade name, manufactured by Horiba Seisakusho Co., Ltd.). The content of the inorganic filler in the resin composition is preferably 5 to 60% by weight, more preferably 5 to 30% by weight, based on 100% by weight of the nonvolatile component of the resin composition. When the content of the inorganic filler is less than 5% by weight, effects such as viscosity control, modulus of elasticity, strength, and thermal expansion tend to be insufficient. When the content of the inorganic filler exceeds 60% by weight, The flexibility of the cured product of the cured product is deteriorated and tends to be broken.

An organic filler may be added to the resin composition of the present invention, if necessary. Examples of the organic filler include acrylic rubber particles and silicone particles. The organic filler preferably has an average particle diameter of not more than 3 mu m, more preferably not more than 1.5 mu m, and further preferably not more than 1 mu m.

In the resin composition of the present invention, various resin additives, resin components other than the components (A) and (B), and the like may be blended to the extent that the effects of the present invention are exerted. Examples of the resin additive include a thickener such as allene (manufactured by Shiroishi Kogyo Co., Ltd.) and bentone (manufactured by Reox Corporation), a silicon-based, fluorine- or acrylic- based defoaming agent, a leveling agent, an imidazole- A surface treating agent such as a silane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black, a phosphorus containing compound, a bromine containing compound, aluminum hydroxide, magnesium hydroxide Antioxidants such as flame retardants, phosphorus antioxidants and phenol antioxidants.

The resin composition of the present invention can be used for solder resist ink, adhesive film, adhesive film with metal foil, coverlay film, prepreg, and prepreg with metal foil.

(Solder resist ink)

By dissolving or dispersing the resin composition of the present invention in various organic solvents to give a paste, a solder resist ink necessary for forming an insulating protective film of a printed circuit board can be produced. The organic solvent used herein is not particularly limited, but it is preferable to use a solvent having a boiling point of 150 ° C or higher, and more preferably a solvent having a boiling point of 180 ° C or higher. When a solvent having a boiling point lower than 150 캜 is used, there is a possibility that the solder resist ink dries on the screen during the application of the ink to clog the screen mesh. Examples of the solvent having a boiling point of 150 ° C or higher include N, N'-dimethylformamide, N, N'-diethylformamide, N, N'-dimethylacetamide, Nitrogen-containing compound solvents such as tetramethylurea, sulfur-containing compound solvents such as dimethylsulfoxide, cyclic ester compound solvents such as? -Butyrolactone, ketone such as cyclohexanone, methylcyclohexanone and isophorone An ether solvent such as a solvent, diglyme and triglyme, and an ester solvent such as carbitol acetate and propylene glycol monoethyl ether acetate. These solvents may be used by mixing two or more kinds. If necessary, nonpolar solvents such as aromatic hydrocarbons may be appropriately mixed and used. For example, petroleum naphtha having a boiling point of 160 ° C or higher may be used.

In order to form an organic solvent optionally in the resin composition of the present invention in the form of a paste, a polyimide resin (A) containing a siloxane structure and (B) a thermosetting resin, a solvent, a curing agent, a curing accelerator, a filler, And then kneading the mixture with a planetary mixer, three rolls, a bead mill, etc., and dissolving or dispersing the mixture. When a solid resin is mixed, a solution in which a solid resin is dissolved in an organic solvent is prepared in advance, and then the above kneading operation is carried out.

(Adhesive film)

The resin composition of the present invention can be used in the form of an adhesive film containing a resin composition layer (A layer) and a support film (B layer), which are suitable forms for producing circuit boards. The adhesive film can be produced by a method known to a person skilled in the art. For example, in the same manner as in the solder resist ink preparation method described above, a polyimide resin containing (A) a siloxane structure and (B) a component including a thermosetting resin, a solvent, and a curing agent, a curing accelerator, a filler, . These are kneaded using a planetary mixer, three rolls, a bead mill or the like and dissolved or dispersed to prepare a resin composition varnish. Subsequently, the resin varnish is coated on the support film, and finally the organic solvent is dried by heating or hot air blowing to form a resin composition layer, whereby an adhesive film can be produced. The support film serves as a support for the production of the adhesive film and is finally peeled off or removed in the production of the printed circuit board. As the support film, there can be used, for example, a polyester such as polyethylene, polyolefin such as polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate, polycarbonate, Metal foil such as foil, and the like.

The thickness of the resin composition layer (A layer) differs depending on the use of the adhesive film. When used in the manufacture of a multilayer flexible circuit board by the build-up method, since the thickness of the conductor layer forming the circuit is 5 to 70 μm, the thickness of the A layer corresponding to the interlayer insulating layer is 10 to 100 Mu m. The thickness of the support film is not particularly limited, but is preferably 10 to 150 mu m, more preferably 25 to 50 mu m.

The solvent for preparing the varnish is not particularly limited. Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve, Carbitols such as benzyl alcohol and butyryl, cyclic ester compounds such as? -Butyrolactone, aromatic hydrocarbons such as toluene, xylene and petroleum naphtha, dimethylformamide, dimethylacetamide and N-methylpyrrolidone . Among these, from the viewpoint of improving the drying of the solvent at the time of film production, the boiling point is preferably 160 캜 or lower, and more preferably 100 캜 or lower. These solvents may be used in combination of two or more kinds.

The drying conditions are not particularly limited, but it is important that the curing of the thermosetting resin composition during drying is not proceeded as far as possible in order to keep the adhesive ability. Further, if a large amount of the organic solvent remains in the adhesive film, it causes the expansion after curing. Therefore, the organic solvent is dried so that the proportion of the organic solvent in the resin composition layer is 5 wt% or less, preferably 3 wt% or less. The specific drying conditions vary depending on the curing properties of the thermosetting resin composition and the amount and the boiling point of the solvent in the varnish. For example, in a varnish containing 30 to 60% by weight of the solvent, the drying is carried out at 80 to 120 ° C for 3 to 15 minutes . Those skilled in the art will be able to set suitably suitable drying conditions by simple experimentation.

(Adhesive film with metal foil)

The resin composition of the present invention can be used in the form of an adhesive film containing a resin composition layer (A layer) and a metal foil (C layer), which are suitable forms for producing circuit boards. The metal foil-attached adhesive film can be produced by a method known to a person skilled in the art. For example, the adhesive film may be laminated with a metal foil. Alternatively, the support of the support film of the above-described adhesive film may be composed of a metal foil, and another support may be laminated on the resin composition layer (A layer) formed on the metal foil. Here, the kind of the metal foil to be used for the metal foil-bonded film of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel, beryllium-copper alloy, phosphor bronze or the like can be used. Copper foil is preferable. As the copper foil, either a rolled copper foil or an electrolytic copper foil may be used, or a copper foil with a carrier may be used.

(Coverlay film)

By using the resin composition of the present invention in the form of an adhesive film containing a resin composition layer (layer A) and a heat-resistant film (layer D), which are suitable forms for producing a circuit board, You can make the necessary coverlay film. The coverlay film may be prepared by preparing a varnish obtained by dissolving the resin composition of the present invention in an organic solvent according to a method known to a person skilled in the art, applying the resin varnish to the heat resistant film, And drying the organic solvent to form a resin composition layer. The heat-resistant film serves as a support for the production of a coverlay film. However, unlike the case of the above-mentioned adhesive film, in the production of a printed circuit board, a situation is finally reached in which the layer is laminated on the outermost layer circuit of the circuit board. Examples of the heat resistant film include polyester such as PET and polyethylene naphthalate, polyimide, polyetherimide, polyamideimide, polyamide, polyetheretherketone, polyether sulfone, liquid crystal polymer and the like.

The appropriate thickness of the resin composition layer (A) depends on the thickness of the conductor layer forming the circuit, but if the thickness of the conductor layer is 5 to 70 mu m, the thickness of the A layer corresponding to the interlayer insulating layer is in the range of 10 to 100 mu m . The thickness of the heat-resistant film is not particularly limited, but is preferably in the range of 10 to 100 占 퐉, and more preferably in the range of 15 to 50 占 퐉. Examples of the solvent for preparing the varnish include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Carbitol and butyl carbitol; cyclic ester compounds such as? -Butyrolactone; aromatic hydrocarbons such as toluene, xylene and petroleum naphtha; dimethylformamide; dimethylformamide; dimethylformamide; Acetamide, N-methylpyrrolidone, and the like. Among these, from the viewpoint of improving the drying of the solvent at the time of film production, the boiling point is preferably 160 캜 or lower, and more preferably 100 캜 or lower. These solvents may be used in combination of two or more kinds.

The drying conditions are not particularly limited, but it is important that the curing of the thermosetting resin composition during drying is not proceeded as far as possible in order to keep the adhesive ability. Further, if a large amount of the organic solvent remains in the adhesive film, it causes the expansion after curing. Therefore, the organic solvent is dried so that the proportion of the organic solvent in the resin composition layer is 5 wt% or less, preferably 3 wt% or less. The specific drying conditions vary depending on the curing properties of the thermosetting resin composition and the amount and the boiling point of the solvent in the varnish. For example, in a varnish containing 30 to 60% by weight of the solvent, the drying may be performed at 80 to 120 캜 for 3 to 15 minutes It is preferable to dry it. Those skilled in the art will be able to set suitably suitable drying conditions by simple experimentation.

(Prepreg)

The prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention to a sheet type reinforcing base material containing fibers by a hot-melt method or a solvent method, and semi-curing the mixture by heating. That is, the thermosetting resin composition of the present invention can be a prepreg impregnated with a sheet-like reinforcing base material containing fibers. It is also possible to prepare an adhesive film containing a thermosetting resin composition as described below from both sides of the sheet-like reinforcing material by laminating. As the sheet-like reinforcing base material containing fibers, for example, those commonly used as prepreg fibers such as glass cloth and aramid fiber can be used.

The hot-melt method is a method in which the resin is temporarily coated on a coated paper having good releasability, the resin is laminated on a sheet-like reinforcing substrate, or the resin is directly laminated on a sheet-like reinforcing substrate by a die coater without dissolving the thermosetting resin composition of the present invention in an organic solvent And then the prepreg is produced. The solvent method is a method in which a sheet-like reinforcing base material is immersed in a resin varnish obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent, such as an adhesive film, the resin varnish is impregnated into the sheet-like reinforcing base material, and then dried.

(Prepreg with metal foil)

A prepreg with a metal foil is a laminate of a prepreg impregnated with the resin composition of the present invention on a metal foil. The production method thereof is not particularly limited. For example, the sheet-like reinforcing base material impregnated with the resin varnish may be bonded to the metal foil and then dried. In addition, a prepreg with a metal foil can be produced by laminating a pre-fabricated prepreg between a releasable film and a metal foil. Here, the kind of the metal foil used in the metal foil prepreg of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel, beryllium-copper alloy, phosphor bronze and the like can be used. In general, a copper foil is used in many cases as the metal foil. As the copper foil, any of rolled copper foil, electrolytic copper foil and carrier-bonded ultra-thin copper foil may be used.

In the adhesive film, the adhesive film with a metal foil, the coverlay film, the prepreg, and the prepreg with a metal foil, a protective film according to the support may be laminated on the surface of the resin composition layer on which the support is not adhered. The thickness of the protective film is not particularly limited, but is preferably 1 to 40 mu m, more preferably 10 to 30 mu m. By laminating a protective film, it is possible to prevent adhesion and scratching of dust or the like to the surface of the resin composition layer. They may also be rolled up and stored.

The solder resist ink, the coverlay film, and the adhesive film can be used to form the outermost insulating protective film. Further, in the case of the adhesive film, the adhesive film with a metal foil, the prepreg, and the prepreg with a metal foil, it can be used for forming a multilayer substrate other than the outermost layer.

(Production of Printed Circuit Board Having Insulation Protective Film on Outermost Layer)

≪ Preparation of insulating protective film by solder resist ink >

The solder resist ink of the present invention can be suitably used particularly for the production of a flexible circuit board. Specifically, a flexible printed wiring board in which the solder resist ink of the present invention is applied to a predetermined portion of the flexible printed wiring board and the coated surface is dried, whereby the entire surface or a part of the surface is protected with the solder resist of the present invention can be obtained. Drying conditions can be suitably set by those skilled in the art depending on the kind of the solder resist to be used, but it is necessary that at least the solvent constituting the solder resist ink is sufficiently dried and the resin composition is thermally cured sufficiently. It is preferable to dry at 100 to 200 DEG C for 1 to 120 minutes. The thickness of the surface protective film to be formed is not particularly limited, but is preferably 5 to 100 占 퐉. The type of the flexible printed wiring board whose surface is protected by the resin composition of the present invention is not particularly limited. For example, the resin composition of the present invention can be used for protection of various flexible printed wiring boards such as TAB flexible printed wiring boards, COF flexible printed wiring boards, multilayer flexible printed wiring boards, and conductive paste printed flexible printed wiring boards. The resin composition of the present invention can be suitably used particularly for TAB flexible printed wiring boards and COF flexible printed wiring board overcoats.

<Fabrication of insulating protective film by coverlay film>

The coverlay film of the present invention can be suitably used particularly in the production of a flexible circuit board. Specifically, the coverlay film of the present invention is first bonded to a predetermined portion of a flexible printed wiring board by a method such as lamination using a vacuum laminator or press lamination using a metal plate. Subsequently, by curing the resin composition layer (A), it is possible to obtain a flexible printed wiring board whose entire surface or a part of its surface is protected by the coverlay film of the present invention. The pressing conditions at this time can be suitably set by a person skilled in the art depending on the type of the coverlay film to be used. The laminate is preferably laminated at a temperature of 100 to 200 DEG C, a pressure of 1 to 40 kgf / cm &lt; 2 &gt;, and an air pressure of 20 mmHg or less. The laminate may be of a batch type or a roll type continuous type. The curing conditions can be appropriately set by a person skilled in the art depending on the type of the resin composition layer (A) to be used. However, the curing conditions need to be such that at least the resin composition sufficiently thermally cures, Lt; / RTI &gt;

&Lt; Preparation of insulating protective film by adhesive film &

The adhesive film of the present invention may be suitably used as an insulating protective film for the outermost layer of a circuit board, like the above-described solder resist ink or coverlay film. Specifically, first, the adhesive film of the present invention is bonded to a predetermined portion of a flexible printed wiring board using a method such as lamination using a vacuum laminator or press lamination using a metal plate. Subsequently, after the support film (B) is peeled, the resin composition layer (A) is cured to obtain a flexible printed wiring board whose entire surface or part of the surface is protected by the adhesive film of the present invention. The pressing conditions at this time may be suitably set by a person skilled in the art according to the type of the coverlay film to be used, but it is preferable to laminate the laminate at a temperature of 100 to 200 DEG C, a pressure of 1 to 40 kgf / cm2 and an air pressure of 20 mmHg or less Do. The laminate may be of a batch type or a roll type continuous type. The curing conditions can be suitably set by a person skilled in the art according to the type of the resin composition layer (A) to be used. However, at least the conditions for the resin composition to be sufficiently thermosetting are required, It is preferred to cure for 120 minutes.

(Fabrication of multi-layer substrate)

&Lt; Case using adhesive film >

The adhesive film of the present invention can be suitably used particularly in the production of a multilayer flexible circuit board. Specifically, first, the adhesive film of the present invention is bonded to one side or both sides of a prefabricated double-sided flexible circuit board by a method such as lamination using a vacuum laminator or press lamination using a metal plate. Subsequently, the support film layer (B) is peeled off, and another pre-fabricated double-sided flexible circuit substrate is bonded to the exposed surface of the resin composition layer (A) using a vacuum laminator. Subsequently, a multilayer flexible printed wiring board can be obtained by further curing the resin composition layer (A) and finally obtaining conduction between layers by forming a through hole. The pressing conditions at this time can be suitably set by a person skilled in the art depending on the kind of the adhesive film to be used. The laminate is preferably laminated at a temperature of 100 to 200 DEG C, a pressure of 1 to 40 kgf / cm &lt; 2 &gt;, and an air pressure of 20 mmHg or less. The laminate may be of a batch type or a roll type continuous type. The curing conditions may be suitably set by a person skilled in the art depending on the type of the resin composition layer (A) to be used. However, the curing conditions need to be such that at least the resin composition sufficiently thermally cures, Min. &Lt; / RTI &gt; Further, by repeatedly performing the same operation, a highly multilayered circuit board can be obtained. The circuit board to be used may be a combination of a single-sided circuit board and a double-sided circuit board at the same time, and a rigid circuit board using a glass epoxy board or the like and a flexible circuit board may be combined to produce a flexrigid circuit board .

<In the case of using the adhesive film with metal foil>

The metal foil-bonded film of the present invention can be suitably used particularly in the production of a multilayer flexible circuit board. Concretely, the copper foil-bonded film of the present invention is bonded to one surface or both surfaces of a pre-fabricated double-sided flexible circuit board by a method such as lamination using a vacuum laminator or press lamination using a metal plate. Subsequently, a patterning circuit of a copper foil in the outermost layer is formed, and a through hole is formed to obtain electrical continuity between the layers. Thus, a multilayer flexible printed wiring board Can be obtained. The pressing conditions at this time may be suitably easily set by a person skilled in the art according to the type of the adhesive film to be used, but it is preferable to laminate the laminate under a reduced pressure of 100 to 200 DEG C, 1 to 40 kgf / cm2 and air pressure of 20 mmHg or less . The laminate may be of a batch type or a roll type continuous type. The curing conditions may be suitably set by a person skilled in the art depending on the type of the resin composition layer (A) to be used. However, the curing conditions need to be such that at least the resin composition sufficiently thermally cures, Min. &Lt; / RTI &gt; Further, by repeatedly performing the same operation, a highly multilayered circuit board can be obtained. As means for forming an interlayer insulating layer necessary for manufacturing a multilayer circuit board, a metal foil-bonded film and the above-mentioned adhesive film may be used at the same time, or as means for forming an insulating protective film of a circuit formed on the outermost layer of the multilayer substrate , The solder resist ink described above, or a coverlay film or an adhesive film may also be used.

<When a prepreg is used>

Next, a method for producing the multilayered printed circuit board of the present invention using the prepreg of the present invention will be described. As a method of laminating the prepreg of the present invention on one side or both sides of a prefabricated double-sided flexible circuit board, for example, a single sheet or a plurality of sheets of the prepreg may be laminated, And laminating the laminate by a lamination press under pressure and heating conditions. In this case, lamination and curing of the prepreg to the circuit board are performed at the same time, and the pressure is preferably 1 to 40 kgf / cm &lt; 2 &gt;, and the temperature is preferably laminating and curing in the range of 100 to 200 DEG C for 1 to 120 minutes . It is also possible to laminate a prepreg on a circuit board with a vacuum laminator, and then heat-cure it. After the insulating layer is formed as a cured product of the prepreg on the circuit board in this manner, a via hole or a through hole is formed in the insulating layer as necessary, the surface of the insulating layer is matched, Whereby a multilayer printed wiring board can be manufactured.

&Lt; Case using prepreg with metal foil >

The method for producing the multilayered printed circuit board of the present invention using the metal foil-coated prepreg of the present invention is the same as the method for producing the multilayered flexible circuit board using the prepreg described above. By using a prepreg with a metal foil, the metal foil can be used as it is as a conductor layer.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis of polyimide resin)

[Synthesis Example 1]

To a 500 mL separable flask equipped with a reflux condenser, a nitrogen inlet tube and a stirrer, 4,4 '- (hexafluoroisopropylene) -bis- (phthalic acid dianhydride ) (Hereinafter referred to as 6FDA), 69.9 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, diaminosiloxane X-22-9409 (Shin-Etsu Chemical Co., Ltd.) 55.7 parts by mass (amine equivalent 665), 2,6-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -1,5-naphthalenediamine NAP) was added in an amount of 6.7 parts by mass, and the mixture was reacted at 45 DEG C for 2 hours under a nitrogen stream. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination apparatus and that the outflow of water could not be seen, the temperature was further raised and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55% by weight of the polyamide resin (A1) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin was 65.2 wt%, and the HFA group equivalent was 3313 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution. As a result, Mn = 11064 and Mw = 18769 were obtained.

[Synthesis Example 2]

32.0 parts by mass of 6FDA, 28.6 parts by mass of? -Butyrolactone, 28.6 parts by mass of Ipzol 150, and 10.0 parts by mass of toluene were placed in a 500 ml separable flask equipped with a water content determining machine connected to a reflux condenser, , 50.1 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent: 430) and 6.3 parts by mass of HFA-NAP were added, The reaction was carried out with stirring for a period of time. Then, the reaction solution was heated, and the condensed water was azeotropically removed with toluene under a nitrogen stream while keeping the temperature at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was accumulated in the water determination apparatus and that the outflow of water could not be seen, the temperature was further raised and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55% by weight of the polyamide resin (A2) having an HFA group was prepared. Ip sol is an aromatic high boiling point solvent manufactured by Idemitsu Kosan Co., Ltd. In this case, the content of the siloxane structure in the resin is 58.4% by weight and the HFA group equivalent is 3316 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution. As a result, Mn = 23086 and Mw = 35970 were obtained.

[Synthesis Example 3]

3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) was added to a 500 mL separable flask equipped with a reflux condenser, a nitrogen introduction pipe, and a stirrer, 23 mass , 30.9 parts by mass of? -Butyrolactone, 30.9 parts by mass of Ipzol 150, 7 parts by mass of toluene, 49.0 parts by mass of diaminosiloxane KF-8010 (Shin-Etsu Chemical Industries, Ltd.) And the reaction was carried out at 45 DEG C for 1 hour under a nitrogen stream. Then, 3,3'-bis (1-hydroxy-1-trifluoromethyl-2,2,2 -Trifluoroethyl) -4,4'-methylene dianiline (hereinafter referred to as HFA-MDA) was added thereto, and stirring reaction was carried out at 45 ° C for 2 hours. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55% by weight of a polyimide resin (A3) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 64.9% by weight and the HFA group equivalent is 3271 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution, and as a result, Mn = 18914 and Mw = 38256 were obtained.

[Synthesis Example 4]

A 500 mL separable flask equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer was charged with 20 parts by mass of BTDA, 70.9 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X 61.5 parts by mass (amine equivalent 665) and 7.4 parts by mass of HFA-NAP were added and stirred at 45 占 폚 for 2 hours under a nitrogen stream to carry out the reaction . Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A4) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 70.9% by weight and the HFA group equivalent is 2881 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was conducted using this preparation solution, and as a result, Mn = 13135 and Mw = 35245 were obtained.

[Synthesis Example 5]

3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (hereinafter referred to as DSDA) was added to a 500 mL separable flask equipped with a reflux condenser, a nitrogen introducing tube, and a stirrer, 19 22.7 parts by mass of? -Butyrolactone, 22.7 parts by mass of Ipzol 150, 7 parts by mass of toluene, 30.9 parts by mass of diaminosiloxane KF-8010 (Shin-Etsu Chemical Co., Ltd.) Amine equivalent: 430), and the mixture was stirred at 45 DEG C for 1 hour under a nitrogen stream to carry out the reaction. Then, 7.5 parts by mass of HFA-NAP was added and stirred at 45 DEG C for 2 hours to carry out the reaction. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the resultant mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A5) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 55.7% by weight, and the HFA group equivalent is 1810 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption of the hydroxyl group derived from the HFA group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution. As a result, Mn = 27337 and Mw = 50713 were obtained.

[Synthesis Example 6]

To a 500 mL separable flask equipped with a water quantitative flow meter connected to a reflux condenser, a nitrogen introduction tube and a stirrer, 25 parts by mass of 6FDA, 68.1 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, diaminosiloxane X , 1.8 parts by mass of 1,5-diaminonaphthalene (hereinafter referred to as NDA) was added in an amount of 58.4 parts by mass (amine equivalent 665) and -22-9409 (manufactured by Shin-Etsu Chemical Co., The reaction was carried out by stirring at 45 DEG C for 2 hours. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B1) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 70.2% by weight.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. As a result of GPC measurement using this preparation solution, Mn = 15974 and Mw = 30002.

[Synthesis Example 7]

36.0 parts by mass of 6FDA, 19.6 parts by mass of? -Butyrolactone, 29.3 parts by mass of Ipzol 150, and 30.0 parts by mass of toluene were placed in a 500 ml separable flask equipped with a reflux condenser, , 51.5 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 [Shin-Etsu Chemical Co., Ltd.] (amine equivalent: 430) were charged and reacted at 45 ° C for 1 hour under a nitrogen stream, Subsequently, 3.2 parts by mass of NDA, 16.4 parts by mass of? -Butyrolactone and 6.7 parts by mass of Ip sol 150 were added and stirred at 45 占 폚 for 2 hours to carry out the reaction. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B2) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 58.6% by weight.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was conducted using this preparation solution, and as a result, Mn = 33046 and Mw = 67573 were obtained.

[Synthesis Example 8]

23 parts by mass of BTDA, 29.5 parts by mass of? -Butyrolactone, 29.5 parts by mass of Ip sol 150, and toluene were added to a 500 ml separable flask equipped with a reflux condenser, a nitrogen introduction pipe and a stirrer, And 49.1 parts by mass (amine equivalent: 430) of diaminosiloxane KF-8010 (Shin-Etsu Chemical Co., Ltd.) were charged and stirred at 45 占 폚 for 1 hour under a nitrogen stream to carry out the reaction. Subsequently, 2.6 parts by mass of 4,4'-diamino-3,3'-dimethyldiphenylmethane (hereinafter referred to as C-100) was added, and the mixture was stirred at 45 ° C for 2 hours to carry out the reaction. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 50 wt% of a polyimide resin (B3) having no phenol group and HFA group was prepared. In this case, the content of the siloxane structure in the resin is 68.0% by weight.

The obtained polyimide resin varnish was coated on a copper plate and heated from 75 캜 to 120 캜 over 12 minutes and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 Respectively. Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution, and as a result, Mn = 38052 and Mw = 110120.

[Synthesis Example 9]

To a 500 mL separable flask equipped with a reflux condenser, a nitrogen introducing tube and a stirrer, 19 parts by mass of DSDA, 55.2 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (44.1 parts by mass, amine equivalent: 665) was charged and stirred at 45 DEG C for 1 hour under a nitrogen stream to carry out the reaction. 6.3 parts by mass of 3-bis (4-amino-3-hydroxyphenoxy) benzene (hereinafter referred to as AHPB) was added and the reaction was carried out at 45 ° C for 2 hours. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B4) having a phenol group but no HFA group was prepared. In this case, the content of the siloxane structure in the resin is 65.3% by weight, and the OH equivalent is 1,744 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. As a result of GPC measurement using this preparation solution, Mn = 14430 and Mw = 28630.

[Synthesis Example 10]

19 parts by mass of DSDA, 54.5 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, and 10 parts by mass of diaminosiloxane X (trade name, manufactured by Nippon Aerosil Co., Ltd.) were added to a 500 ml separable flask equipped with a water- -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (44.1 parts by mass, amine equivalent: 665) was charged and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out the reaction. Diamino-4,4'-dihydroxydiphenyl sulfone (hereinafter referred to as DABS) was added thereto, and the reaction was carried out by stirring at 45 ° C for 2 hours. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handwriting machine or the water outflow was not observed, the temperature was further raised, and stirring was performed at 200 ° C for 1 hour. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (B5) having a phenol group but no HFA group was prepared. In this case, the content of the siloxane structure in the resin is 66.2 wt%, and the OH equivalent is 1722 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution, and as a result, Mn = 16631 and Mw = 30691.

[Synthesis Example 11]

20 parts by mass of BTDA, 76.5 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (725 parts by mass, amine equivalent 655) was charged and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out the reaction. NAP was added in an amount of 2.7 parts by mass, and the reaction was carried out at 45 DEG C for 2 hours with stirring. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. When it was confirmed that a predetermined amount of water was accumulated in the water determination apparatus and that the outflow of water was not observed, the temperature was further raised, and the mixture was stirred at 200 ° C for 14 hours. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A6) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 78.0% by weight and the HFA group equivalent is 8392 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. As a result of GPC measurement using this preparation solution, Mn = 19275 and Mw = 24410.

[Synthesis Example 12]

20 parts by mass of BTDA, 58.5 parts by mass of? -Butyrolactone, 7 parts by mass of toluene, 10 parts by mass of diaminosiloxane X -22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) (375 parts by mass, amine equivalent 655) was charged and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out the reaction. NAP was added in an amount of 16.4 parts by mass, and the reaction was carried out at 45 DEG C for 2 hours with stirring. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while being held at about 160 ° C. At the time when it was confirmed that a predetermined amount of water was held in the water quantitative handkerchief, and the outflow of water was confirmed, the temperature was further raised, and the mixture was stirred at 200 ° C for 11 hours. Thereafter, the mixture was cooled to completion, and a varnish containing 55 wt% of a polyimide resin (A7) having an HFA group was prepared. In this case, the content of the siloxane structure in the resin is 52.2% by weight, and the HFA group equivalent is 1069 g / mol.

The obtained polyimide resin varnish was coated on a copper plate, heated from 75 캜 to 120 캜 over 12 minutes, and further heated at 180 캜 for 90 minutes to dry. With respect to this coating film, the infrared absorption spectrum was measured by a reflection method. As a result, absorption based on polyamic acid indicating that unreacted functional groups were present was not observed, and absorption based on imide groups was confirmed at 1780 cm ^-1 and 1720 cm ^-1 , And the absorption from the phenolic hydroxyl group was confirmed at 3300 to 3500 cm ^-1 . Further, 36 mg of the obtained polyimide resin varnish was weighed and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved to prepare a total of 5 g. GPC measurement was carried out using this preparation solution, and as a result, Mn = 26629 and Mw = 37452 were obtained.

(Preparation of resin composition)

Epoxy resin, the siloxane-containing polyimide resin synthesized in accordance with Synthesis Examples 1 to 12, and the curing agent, curing accelerator, and inorganic filler, if necessary, were mixed in the blending amounts (expressed as parts by weight of solid content) shown in Tables 1 and 2 , And a centrifugal defoaming mixer (trade name &quot; Awatore Rentero &quot;, manufactured by Shinki) were used to obtain the respective resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7. Further, as the epoxy resin, phenol novolak type epoxy resin EP157 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) or ZX1059 (trade name, manufactured by Toki Chemical Co., Ltd.), which is a mixture of bisphenol A type and bisphenol F type epoxy resin, Respectively. Further, as a curing agent, a dicyclopentadiene-modified phenol resin DPP6115L (manufactured by Shin-Etsu Chemical Co., Ltd.) was used and an imidazole-based P200 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) was used as a curing accelerator , And spherical silica SC4050SX (manufactured by Adomex Co., Ltd.) was used as an inorganic filler. In addition, a solvent was mixed as needed.

(Preparation of Cured Film)

The resin composition obtained was coated on a releasing-treated PET film, heated at 75 to 120 占 폚 for 12 minutes and then heated at 180 占 폚 for 90 minutes to obtain a cured film having a thickness of 40 占 퐉.

(Solvent resistance test)

The cured film was placed on the balance, and the surface of the cured film was observed using a cotton swab containing acetone so that the balance showed a weight of 10 g and rubbed five times by reciprocating. A case in which no change in color of the surface of the cured film was observed was evaluated as &amp; cir &amp;

(Heat resistance test)

With respect to the polyimide resin obtained in Synthesis Example, a resin composition was prepared in the same manner as described above, and was coated on a copper foil-lacquered surface so as to have a thickness in the range of 40 to 100 탆 at the time of drying, and heated at 75 to 120 캜 for 12 minutes And then heated again at 180 DEG C for 90 minutes to obtain a cured film. The copper foil on which the cured film was formed was immersed in a ferric chloride solution for etching removal, and then dried at 100 DEG C for 10 minutes to produce a cured film from which the copper foil was removed. The cured film from which the copper foil was removed was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tenshiron universal testing machine (manufactured by Abrand Co., Ltd.), and the elastic modulus before heat treatment was measured.

On the other hand, the copper foil-cured film obtained by the above method was subjected to (1) heating at 220 DEG C for 30 minutes in air, (2) at 250 DEG C for 30 minutes in air, and (3) Heat treatment was performed. The copper foil-cured film after the heat treatment was immersed in a ferric chloride solution to remove the copper foil by etching, and then dried at 100 ° C for 10 minutes to produce a cured film from which the copper foil was removed. With respect to the cured film from which the copper foil was removed, a tensile test was conducted by a Tenshiron universal testing machine (manufactured by Abrand Co., Ltd., Japan) according to Japanese Industrial Standards (JIS K7127) The elastic modulus of the cured film was measured. Then, the &quot; modulus of elasticity after heat treatment &quot;, and &quot; modulus of elasticity before heat treatment &quot; The difference in the modulus of elasticity after the heat treatment at 270 캜 for 30 minutes in the air and the modulus of elasticity before the heat treatment was regarded as the fluctuation width of the modulus of elasticity.

Table 1 and Table 2 show the results of the heat resistance test and the solvent resistance test of the polyimide resin composition described in the table.

The results of Table 1 and Table 2 will be described below. As shown in Comparative Examples 1 to 3 and 6, the composition containing the siloxane structure-containing polyimide resin having neither the HFA group nor the phenol group had poor solvent resistance. This is thought to be due to the low reactivity of the polyimide resin and the epoxy resin. As shown in Comparative Examples 4, 5 and 7 of Table 1 and Table 2, the composition of the composition containing the siloxane structure-containing polyimide resin having a phenol group had a large change rate of the modulus of elasticity after heat treatment at 250 캜 for 30 minutes , And the fluctuation width of the modulus of elasticity also increases. On the other hand, Examples 1 to 3, 5, 6 and 8, which are compositions containing a siloxane structure-containing polyimide resin having an HFA group, showed a small rate of change in modulus of elasticity after heat treatment at 250 DEG C for 30 minutes, Also, the anti-solvent properties were also excellent. In Examples 4 and 7, the change rate of the modulus of elasticity after heat treatment at 250 DEG C for 30 minutes is large, but the modulus of elasticity itself before heat treatment is a very small value of 60 MPa or less. In the case of Examples 2, 3, 5 and 8, the siloxane content of the siloxane structure-containing polyimide resin having an HFA group is not excessively large, and the rate of change of the modulus of elasticity is small, and the flexibility is excellent.

[Example 9]

(Production of adhesive film A1)

The resin composition of Example 2 was coated on a PET film having a thickness of 38 탆 subjected to release treatment using a die coater so that the thickness after drying was 40 탆. After the application, it was dried at 75 to 120 ° C for 12 minutes to produce an adhesive film A1 having a resin composition layer formed thereon. Then, a polypropylene film having a thickness of 15 mu m was wound on the surface of the resin composition layer while being rolled up in roll form.

[Example 10]

(Production of adhesive film A2)

Using the resin composition of Example 5, an adhesive film A2 was produced in the same manner as in Example 9. [

[Example 11]

(Production of resin-coated copper foil B1)

On the copper foil having a thickness of 12 占 퐉, the resin composition of Example 2 was applied using a die coater so that the thickness after drying was 40 占 퐉. After the application, it was dried at 75 to 120 DEG C for 12 minutes to produce a resin-coated copper foil B1 having a resin composition layer formed thereon. Then, a polypropylene film having a thickness of 15 mu m was wound on the surface of the resin composition layer while being rolled up in roll form.

[Example 12]

(Production of resin-coated copper foil B2)

Using the resin composition of Example 5, the same operations as in Example 11 were carried out to produce a resin-coated copper foil B2.

[Example 13]

(Preparation of Coverage Film)

On the polyimide film having a thickness of 25 탆, the resin composition of Example 2 was applied using a die coater so that the thickness after drying was 35 탆. After the application, it was dried at 75 to 120 DEG C for 12 minutes to form a resin composition layer, thereby preparing a coverlay film. Then, a polypropylene film having a thickness of 15 mu m was wound on the surface of the resin composition layer while being rolled up in roll form.

[Example 14]

(Production of solder resist ink)

In the preparation of the resin composition of Example 2, the solid resin was dissolved in carbitol acetate, which had previously been used as a high boiling point solvent, and then a centrifugal defoaming mixer (trade name "Awatolirentero", manufactured by Shinki) was used Followed by stirring and mixing to prepare a solder resist ink.

[Example 15]

(Production of Flexible Circuit Board P1 and Evaluation of Flexural Durability)

First, the polypropylene film of the coverlay film produced in Example 13 was peeled off. Subsequently, on the circuit surface of the flexible circuit board obtained by using a two-layer CCL (copper clad laminate) composed of a copper layer (thickness 12 占 퐉) and a polyimide film (thickness 20 占 퐉) And laminated under the conditions of a temperature of 130 DEG C, a pressure of 7 kgf / cm &lt; 2 &gt;, and an air pressure of 5 mmHg or less by means of a vacuum laminator (manufactured by Meikishaishakusho Co., Ltd.). Subsequently, the single-sided circuit board P1 was prepared by (1) heating at 120 ° C for 30 minutes and (2) 180 ° C for 90 minutes in order and curing. As a result of carrying out a test of bending the coverlay film face outward by 180 degrees, whitening or the like did not occur in the curved portion of the coverlay film, showing excellent bending property.

[Example 16]

(Production of Flexible Circuit Board P2 and Evaluation of Flexural Durability)

A solder resist ink obtained in Example 14 was applied on a circuit surface of a flexible circuit board obtained by using a two-layer CCL composed of a copper layer (thickness 12 占 퐉) and a polyimide film (thickness 20 占 퐉), using a 200 mesh plate Screen printing, and cured at 180 DEG C for 90 minutes to prepare a single-sided circuit board P2. As a result of performing the test of bending the solder resist surface of the produced single-sided circuit board P2 outward by 180 degrees, the solder resist did not show whitening at the bent portion of the solder resist and showed good bendability.

[Example 17]

(Production of Multilayer Flexible Circuit Substrate MP1 and Measurement of Peel Strength)

First, the polypropylene film of the adhesive film A1 produced in Example 9 was peeled off. Subsequently, the resin composition surface of the adhesive film was faced to the circuit surface of the flexible circuit board obtained by using the two-layer CCL composed of the copper layer (thickness 12 占 퐉) and the polyimide film (thickness 20 占 퐉), and a vacuum laminator Ltd. under the conditions of a temperature of 130 占 폚, a pressure of 7 kgf / cm2, and an air pressure of 5 mmHg or less. Thereafter, the release-treated PET film of the laminated adhesive film was peeled off, and the M surface of a copper foil having a thickness of 18 mu m was faced to the surface of the resin composition surface, and the surface was again exposed to a vacuum laminator (manufactured by Meikishaishakusho Co., Ltd.) At a temperature of 130 캜, a pressure of 7 kgf / cm 2, and an air pressure of 5 mmHg or less. Then, the multilayer flexible circuit substrate MP1 was further subjected to heat treatment at 120 DEG C for 30 minutes and then at 180 DEG C for 90 minutes. The peel strength of the conductor layer (corresponding to the S face of copper foil) on the circuit board MP1 and the adhesive film was 0.94 kgf / cm, and had a strong adhesive property. The peel strength measurement was carried out in accordance with JIS C6481.

[Example 18]

(Production of Multilayer Flexible Circuit Substrate MP2 and Measurement of Peel Strength)

First, the polypropylene film of the adhesive film A2 obtained in Example 10 was peeled off. Subsequently, the resin composition surface of the adhesive film was faced to the circuit surface of the flexible circuit board obtained by using the two-layer CCL composed of the copper layer (thickness 12 占 퐉) and the polyimide film (thickness 20 占 퐉), and a vacuum laminator Ltd. under the conditions of a temperature of 130 占 폚, a pressure of 7 kgf / cm2, and an air pressure of 5 mmHg or less. Thereafter, the release-treated PET film of the laminated adhesive film was peeled off, and the M surface of a copper foil having a thickness of 18 mu m was faced to the surface of the resin composition surface. Then, a vacuum laminate (manufactured by Takeuchi Kikai Co., Ltd.) At a temperature of 130 캜, a pressure of 7 kgf / cm 2, and an air pressure of 5 mmHg or less. Then, the multilayer flexible circuit substrate MP2 was then subjected to heat treatment at 120 캜 for 30 minutes and at 180 캜 for 90 minutes in this order. The peel strength of the conductor layer (corresponding to the S face of copper foil) on the circuit board MP2 and the adhesive film was 1.05 kgf / cm, and had a strong adhesive property. The peel strength measurement was performed in accordance with JIS C6481.

[Example 19]

(Manufacture of multilayer flexible circuit board MP3)

First, the polypropylene film of the resin-coated copper foil B1 obtained in Example 11 was peeled off. Subsequently, the resin composition surface of the resin-coated copper foil B1 was faced to the circuit surface of the flexible circuit board obtained by using the two-layer CCL composed of the copper layer (thickness 12 占 퐉) and the polyimide film (thickness 20 占 퐉) Was laminated under the conditions of a temperature of 130 DEG C, a pressure of 7 kgf / cm &lt; 2 &gt;, and an air pressure of 5 mmHg or less by means of a vacuum laminator (manufactured by Meiji Seisakusho Co., Ltd.). Thereafter, heat treatment was performed at 120 캜 for 30 minutes and then at 180 캜 for 90 minutes to produce a multilayer flexible circuit board MP3.

[Example 20]

(Production of Multilayer Flexible Circuit Substrate MP4)

First, the polypropylene film of the resin-coated copper foil B2 obtained in Example 12 was peeled off. Subsequently, the resin composition surface of the resin-coated copper foil B2 was faced to the circuit surface of the flexible circuit board obtained by using the two-layer CCL composed of the copper layer (thickness 12 mu m) and the polyimide film (thickness 20 mu m) Was laminated under the conditions of a temperature of 130 DEG C, a pressure of 7 kgf / cm &lt; 2 &gt;, and an air pressure of 5 mmHg or less by means of a vacuum laminator (manufactured by Meiji Seisakusho Co., Ltd.). Thereafter, heat treatment was performed at 120 캜 for 30 minutes and then at 180 캜 for 90 minutes in order to produce a multilayer flexible circuit board MP4.

This application is based on Japanese Patent Application No. 2008-288152, the contents of which are all incorporated herein by reference.

Claims (21)

(A) a polyimide resin having a hexafluoroisopropanol group and a siloxane structure, and (B) a thermosetting resin, wherein the polyimide resin has a repeating unit represented by the following general formulas (1) and (2) .
Formula 1

(2)

In the above Formulas 1 and 2,
R1 is a tetravalent organic group,
R2 is a divalent diamine residue having a hexafluoroisopropanol group,
R3 is a divalent siloxane diamine residue,
The repeating number M in one molecule of the repeating unit represented by the formula (1) is an integer of 1 to 100,
The repeating number N in one molecule of the repeating unit represented by the general formula (2) is an integer of 1 or more and 100 or less. The resin composition for a printed wiring board according to claim 1, further comprising (C) an inorganic filler. The resin composition for a printed wiring board according to claim 1 or 2, wherein the thermosetting resin is an epoxy resin. delete The printed wiring board according to any one of claims 1 to 4, wherein the hexafluoroisopropanol group (A) and the hexafluoroisopropanol group of the polyimide resin having a siloxane structure have a functional group equivalent of 1000 to 10000 g / mol Resin composition. The resin composition for a printed wiring board according to claim 1 or 2, wherein the polyimide resin (A) having a hexafluoroisopropanol group and a siloxane structure has a siloxane content of 50 to 80% by weight. A solder resist ink containing the resin composition according to claim 1 or 2. An adhesive film comprising the resin composition according to claim 1 or 2 layered on a support. An adhesive film with a metal foil, wherein the resin composition according to claim 1 or 2 is layered on a metal foil. A prepreg obtained by impregnating a sheet-like fibrous substrate with the resin composition according to any one of claims 1 to 3. A prepreg with metal foil, wherein a metal foil is laminated on the prepreg according to claim 10. A coverlay film wherein the resin composition according to claim 1 or 2 is layered on a heat resistant film. Wherein the insulating layer contains the resin composition for a printed wiring board according to any one of claims 1 to 3. 14. The printed wiring board according to claim 13, wherein the insulating layer comprises a solder resist layer, an interlayer insulating layer and a coverlay layer. A solder resist layer formed by the solder resist ink according to claim 7. A printed wiring board in which a solder resist layer is formed by the adhesive film according to claim 8. A printed wiring board in which an interlayer insulating layer is formed by the adhesive film according to claim 8. An printed wiring board in which an interlayer insulating layer and / or a conductor layer is formed by the adhesive film with a metal foil according to claim 9. A printed wiring board in which an interlayer insulating layer is formed by the prepreg according to claim 10. A printed wiring board in which an interlayer insulating layer and / or a conductor layer is formed by the metal foil-coated prepreg according to claim 11. A printed wiring board in which a coverlay layer is formed by the coverlay film according to claim 12.